US4506083A - Thioxanthonecarboxylic acid esters, thioesters and amides - Google Patents

Thioxanthonecarboxylic acid esters, thioesters and amides Download PDF

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US4506083A
US4506083A US06/392,922 US39292282A US4506083A US 4506083 A US4506083 A US 4506083A US 39292282 A US39292282 A US 39292282A US 4506083 A US4506083 A US 4506083A
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thioxanthone
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alkyl
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Vratislav Kvita
Hans Zweifel
Martin Roth
Louis Felder
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Novartis Corp
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Ciba Geigy Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/122—Sulfur compound containing
    • Y10S430/123—Sulfur in heterocyclic ring

Definitions

  • the present invention relates to novel Thioxanthone-carboxylic acid esters, thioesters and amides, processes for their preparation and their use as sensitisers for photocrosslinkable polymers or as initiators, if desired as a mixture with aminos, for the photopolymerisation of ethylenically unsaturated compounds or for photochemical crosslinking of polyolefines.
  • thioxanthone is suitable as a sensitiser for photo-induced crosslinking reactions.
  • the prerequisite for a successful application of this type is good compatibility of the sensitiser in the polymer, i.e. the sensitiser must be miscible in up to fairly high concentrations with the polymer.
  • the sensitisers must be readily soluble in the solvents used when processing the polymers.
  • Unsubstituted thioxanthone which is a known compound, does not satisfy these requirements in all respects; in particular, it easily separates in the polymer, as a result of which its sensitiser effect is severely impaired.
  • Novel thioxanthone derivatives have now been found which are outstandingly suitable for use as sensitisers for photocrosslinkable polymers, in that they meet in full the abovementioned requirements with respect to compatibility with the polymer and solubility in conventional organic solvents. Moreover, suprisingly, UV absorption can be so influenced by the novel thioxanthone derivatives according to the invention that these exert a sensitising action even on irradiation with long-wave UV light (up to 450 nm) and thus effect crosslinking of the photosensitive polymers.
  • mixtures of thioxanthone derivatives according to the invention with organic amines as initiators for the photopolymerisation of ethylenically unsaturated compounds, or for photochemical crosslinking of polyolefines are distinguished by a higher polymerisation rate, by a lower tendency to yellowing in the case of coatings containing white pigment, by better solubility in the substrate and/or by increased stability on storage.
  • thioxanthonecarboxylic acid esters, thioesters and amides have the formula I ##STR2## in which X is hydrogen, halogen, --CN, --OH, --SH, --NH 2 , --NO 2 , --SO 3 H, phenylsulfonyl or alkylsulfonyl, alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or --CO--alkyl, each having 1-4 C atoms in the alkyl moieties, --CO--OR 1 , --CO--SR 1 , --CO---N(R 1 )(R 2 ), --CO--piperidyl, --CO--pyrrolidinyl or --CO--morpholinyl, Z is hydrogen, halogen, --OH, --SH or alkyl, alkoxy, alkylthio or dialkylamino having 1-4 C atoms in the alkyl moieties,
  • Alkyl, alkoxy and alkylthio groups X, Z, R 1 and R 2 and alkyl moieties in the radicals X or Z can be straight-chain or branched.
  • Examples or alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylsulfonyl, N-alkylamino, N,N-dialkylamino and --CO--alkyl groups X, Z, R 1 or R 2 according to the definition are: the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, n-pentyl, 2- or 3-pentyl, n-hexyl, n-heptyl, 2- or 3-heptyl, n-octyl, n-nonyl, n-decyl, 2-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, tridec-7-yl, heptadec-9-yl, 2,6,10-trimethyldode
  • R 1 and R 2 in a CO--OR 1 , --CO--SR 1 or --CO--N(R 1 )(R 2 ) group X preferably have the same meaning as in the radicals Y.
  • R 1 is preferably alkyl having a total of 1 to 18 and in particular 1-12 C atoms, cyclohexyl or alkoxyalkyl having 3-8 C atoms.
  • Preferred compounds of the formula I are those in which X is hydrogen, or X and Z are hydrogen, and the group --CO--Y is bonded in the 1-position or 3-position.
  • a further category of preferred compounds of the formula I comprises those in which Y is --OR 1 or --N(R 1 )(R 2 ) and especially those in which Y is --OR 1 and R 1 is alkyl having 1-18 C atoms, cyclohexyl or alkoxyalkyl having 3-8 C atoms.
  • Particularly preferred compounds of the formula I are those in which X is hydrogen, Z is hydrogen, chlorine, alkyl or alkoxy, the group --CO--Y is bonded in the 1-position or 3-position and Y is alkoxy having 1-18 C atoms, alkoxyalkyl having 3-6 C atoms or alkylamino or dialkylamino having 1-4 C atoms in the alkyl moiety.
  • the compounds of the formula I can be prepared, for example, by cyclising a compound of the formula IIa or IIb ##STR3## in which Z is as defined under formula I, X 1 is hydrogen, halogen, --CN, --OH, --SH, --NO 2 , --SO 3 H, --COOH, phenylsulfonyl or alkylsulfonyl, alkyl, alkoxy, alkylthio, N,N-dialkylamino or --CO--alkyl, each having 1-4 C atoms in the alkyl moieties, --CO--OR 1 or --CO--SR 1 and R 1 is as defined under forumla I, and R and R' are --OH, or, if the two --COR groups are in the ortho-position relative to one another, the two Rs together are --O--, to give a compound of the formula III ##STR4## reacting the compound of the formula III, if desired after prior conversion to the corresponding acid chloride, with a compound HY and
  • the starting material used is a compound of the formula IIa in which the two --COR groups are in the ortho-position or para-position, and by this means intermediates of the formula III are obtained in which the carboxyl group is in the 1-position or 3-position.
  • compounds of the formula Ia ##STR5## in which Z' is hydrogen, halogen or alkyl, alkoxy, alkylthio or dialkylamino, each having 1-4 C atoms in the alkyl moieties, can also be obtained by either (a) cyclising a compound of the formula Va ##STR6## in which X 2 is hydrogen, halogen, --CN, NO 2 , --SO 3 H, --COOH, phenylsulfonyl or alkylsulfonyl, alkyl, alkoxy, alkylthio or dialkylamino, each having 1-4 C atoms in the alkyl moieties, and one of R 3 and R 4 is a mercapto group and the other is a detachable group, to give a compound of the formula VI ##STR7## or (b) reacting a compound of the formula Vb ##STR8## in which R 5 and R 6 independently of one another are a detachable
  • Chlorinating agents which can be used are, for example, thionyl chloride, PCl 5 or oxalyl chloride. Carboxyl groups X 1 or X 2 ' are also chlorinated during this reaction.
  • the intermediates of the formula VI or III can also be converted to compounds of the formula I by converting the said compounds to a corresponding alkali metal salt or alkaline earth metal salt, reacting the resulting salt with a compound of the formula Hal-Y, in which Y is as defined under formula I and Hal is a halogen atom, to give a compound of the formula I and, if desired, subsequently converting the groups X 1 or X 2 ' to a group X which differs from X 1 or X 2 '.
  • An excess of the compound Hal-Y can also serve as the solvent.
  • the said reaction can also be carried out by means of phase transfer catalysis, for example in the presence of tetraalkylammonium halides or trialkylbenzylammonium halides, such as tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride or triethylbenzylammonium chloride.
  • tetraalkylammonium halides or trialkylbenzylammonium halides such as tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride or triethylbenzylammonium chloride.
  • compounds of the formula Ib ##STR10## in which X 3 is a group corresponding to X but is not --CN, and Y and Z' are as defined under formula I or Ia, can also be prepared by reacting a compound of the formula IX ##STR11## in the presence of a Friedel-Crafts catalyst with a compound of the formula ##STR12## decomposing the resulting complex to give a compound of the formula XI ##STR13## in which X 3 ' is hydrogen, halogen, --NO 2 , --COOH, --SO 3 H, phenylsulfonyl or alkylsulfonyl, alkyl, alkoxy, alkylthio, N,N-dialkylamino or --CO--alkyl, each having 1-4 C atoms in the alkyl moieties, --CO--OR 1 or --CO--SR 1 , reacting the compound of the formula XI, if desired after prior conversion to the acid chloride, with
  • the cyclisation of the compounds of the formula IIa and IIb to give compounds of the formula III is advantageously carried out in the presence of a proton acid or of a Lewis acid.
  • suitable proton acids are polyphosphoric acid, which can be mixed with phosphorus oxychloride, and chlorosulfonic acid and sulfuric acid.
  • suitable Lewis acids are aluminium trichloride or boron trifluoride. Cyclisation in the presence of a proton acid is preferred.
  • the reaction is preferably carried out at temperatures between about 0° and 240° C. and in particular between about 150° and 210° C.
  • Suitable detachable groups R 3 to R 6 are in particular halogen atoms and nitro, arylsulfonyl and sulfinyl groups.
  • Preferred detachable groups R 3 to R 6 are halogen atoms, especially chlorine, and nitro groups.
  • the inorganic sulfide used for the reaction with compounds of the formula Vb is advantageously an alkali metal sulfide or hydrosulfide or alkaline earth metal sulfide or hydrosulfide, preferably sodium sulfide.
  • the reaction temperatures for the cyclisation of the compounds of the formula Va and the reaction of the compounds of the formula Vb with an inorganic sulfide are advantageously between about 20° and 350° C.
  • the reaction is preferably carried out in an organic solvent, in particular in an aprotic solvent.
  • Suitable solvents are, for example, dialkylsulfoxides, such as dimethylsulfoxide, N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms, such as N,N-dimethylformamide and N,N-dimethylacetamide, and also N-methylpyrrolidone, hexamethylphosphoric acid triamide and sulfolane. It is also possible to use mixtures with other solvents, such as alcohols, for example 2-methoxyethanol, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
  • the starting materials of the formula Va and Vb can be obtained in a manner known per se, by a Friedel-Craft reaction of correspondingly substituted acyl halides with a suitably substituted nucleophilic aromatic compound.
  • the condensation reaction of the compounds of the formula IX with the compounds of the formula X in the presence of Friedel-Crafts catalysts is advantageously carried out in an organic medium at temperatures between about 10° and 80° C.
  • the reagents are added to the organic medium at a somewhat lower temperature, for example at between about 10° and 40° C. and in particular at between about 15° and 25° C. After all of the reagents, including the catalyst, have been added, the temperature can be raised to about 80° C.
  • Suitable solvents for carrying out the Friedel-Crafts reaction are, for example, chlorinated aliphatic or aromatic hydrocarbons, such as methylene chloride, 1,2-dichloroethane, 1,2,3-trichloropropane, 1,1,2,2-tetrachloroethane and halogenated benzenes, such as dichlorobenzene.
  • chlorinated aliphatic or aromatic hydrocarbons such as methylene chloride, 1,2-dichloroethane, 1,2,3-trichloropropane, 1,1,2,2-tetrachloroethane and halogenated benzenes, such as dichlorobenzene.
  • Suitable Friedel-Crafts catalysts are, for example, aluminium chloride, aluminium bromide, zinc chloride, tin tetrachloride, boron trifluoride, iron-III chloride, titanium tetrachloride, phosphorus trichloride, phosphorus oxychloride, antimony pentafluoride and antimony pentachloride.
  • Aluminum chloride is preferably used.
  • the resulting complex can be decomposed by pouring into a water/ice mixture or by adding dilute mineral acid, such as hydrochloric acid, or aqueous alkali metal hydroxide or alkaline earth metal hydroxide solutions, such as sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide.
  • dilute mineral acid such as hydrochloric acid
  • aqueous alkali metal hydroxide or alkaline earth metal hydroxide solutions such as sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide.
  • reaction of the compounds of the formula III or VI with a compound of the formula HY can, depending on the nature of the reactants, be carried out with or without the addition of an inert organic solvent, such as dioxan, methylene chloride, chloroform, acetone, benzene or toluene, and if desired can be carried out in the presence of an organic base, for example triethylamine or pyridine.
  • an inert organic solvent such as dioxan, methylene chloride, chloroform, acetone, benzene or toluene
  • an organic base for example triethylamine or pyridine.
  • the solvent used is advantageously an excess of the corresponding alcohol or thiol.
  • the preparation of the amides is preferably carried out in the presence of an inert organic solvent and of an excess of the corresponding amine.
  • the reaction with alcohols is advantageously carried out under reflux.
  • the reaction temperatures for the reaction with thiols are in general between about 25° and 80° C., whilst the reaction with the amines is preferably carried out at between about 0° and 40° C.
  • the reaction of the free acids of the formula III or VI is advantageously carried out in the presence of a dehydrating agent, such as HCl gas or concentrated sulfuric acid, and if desired with removal of the water as an azeotrope.
  • Compounds of the formula I in which Y is --NHR 1 , and R 1 is alkyl as defined, can also be prepared by reacting carboxylic acid esters of the formula I, preferably the methyl or ethyl esters, with amines R 1 NH 2 in the presence of suitable solvents, such as dioxan, tetrahydrofuran, methanol, ethanol, benzene or toluene.
  • suitable solvents such as dioxan, tetrahydrofuran, methanol, ethanol, benzene or toluene.
  • groups X 1 , X 2 ' and X 3 ' to groups X and X 3 can be carried out in a manner known per se.
  • nitro groups X 1 , X 2 ' or X 3 ' can be reduced by methods known per se to amino groups, which, in turn, can be converted to halogen atoms, --OH, --SH, --CN or alkoxy, N-alkylamino or N,N-dialkylamino groups.
  • Cyano groups X 1 or X 2 can be converted to --CO--alkyl groups.
  • carboxyl groups X 1 , X 2 ' and X 3 ' are converted to --CO--OR 1 , --CO--SR 1 , --CO--N(R 1 )(R 2 ), --CO--piperidyl, --CO--pyrrolidinyl or --CO--morpholinyl groups X.
  • Thioxanthones of the formula I which are substituted by alkylsulfonyl or phenylsulfonyl groups can be prepared, for example, by reacting the corresponding nitro compounds with alkali metal alkylsulfinates or alkali metal phenylsulfinates.
  • the starting compounds of the formulae IX and X are known or can be prepared by methods known per se.
  • Compounds of the formula IIa and IIb can, for example, be prepared by a process analogous to that described in German Offenlegungsschrift No. 2,344,799, by reacting suitably substituted thiophenols or derivatives thereof, such as alkali metal salts or alkaline earth metal salts, with nitro- or halogeno-benzenes.
  • the thiophenol and the nitro- or halogeno-benzene together must contain at least two --COR or --COR' groups, or two groups which can be converted to --COR or --COR' groups, such as nitrile groups, one of which must be in the ortho-position relative to the SH group or to the nitro group or to the halogen atom.
  • a halogeno-benzene is used for the reaction, the formation of the diphenyl thioether of the formula IIa or IIb is advantageously effected by heating the reactants in the presence of NaOH or KOH in a high-boiling polar solvent, such as N,N-dimethylformamide or N,N-dimethylacetamide.
  • Suitable halogenobenzenes are, for example, 2-, 3- and 4-chlorobenzoic acid.
  • Suitable nitrobenzenes are those which also contain, in addition to the nitro group, one or more electron-attracting groups, such as carboxylic acid ester groups, carboxylic acid chloride groups, nitrile groups, anhydride groups or imide groups.
  • electron-attracting groups such as carboxylic acid ester groups, carboxylic acid chloride groups, nitrile groups, anhydride groups or imide groups.
  • Examples of such nitrobenzenes are: phthalic anhydride, phthalic acid dinitrile, N-phenyl- or N-ethyl-nitrophthalimide, isophthalic acid dinitrile, terephthalic acid dinitrile, isophthalic acid dichloride, terephthalic acid dichloride and dialkyl esters of isophthalic acid and terephthalic acid, having 1-8 C atoms in the alkyl moieties in each case.
  • esters of the formula XIII ##STR15## are reacted, in the presence of a base, with thiophenols of the formula XIV ##STR16## to give compounds of the formula XV ##STR17## in which formula X 1 and Z are as defined above and the Qs independently of one another are alkyl having 1-8 C atoms or phenyl.
  • the two Qs have the same meaning and are alkyl having 1-6 C atoms.
  • the above reaction is advantageously carried out in the presence of an inert organic solvent, such as N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms, for example N,N-dimethylformamide or N,N-dimethylacetamide, dimethylsulfoxide or hexamethylphosphoric acid amide.
  • Suitable bases are, for example, alkali metal hydrides or hydroxides and alkaline earth metal hydrides or hydroxides, in particular sodium hydride, sodium hydroxide and potassium hydroxide.
  • the compounds of the formula XV are subsequently saponified in a manner known per se to give compounds of the formula IIa.
  • the intermediates of the formula XV are novel with the exception of those in which X 1 and Z are each hydrogen and the two Qs are methyl and the --COOQ groups are in the m-position or p-position relative to one another. These novel compounds of the formula XV are likewise a subject of the invention.
  • the thioxanthone derivatives of the formula I are used as photoinitiators.
  • the invention therefore also relates to the use of compounds of the formula I as initiators for the photopolymerisation of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefines, and also to mixtures of (A) a compound of the formula I and (B) an organic amine, as initiators for the photopolymerisation of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefines.
  • the organic amines used can be aliphatic, aromatic, araliphatic, cycloaliphatic or heterocyclic amines. They can be primary, secondary or tertiary amines. Examples are butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, di-cyclohexylamine, triethylamine, phenyl-diethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, ethyl p-dimethylaminobenzoate or Michler's ketone (4,4'-bis-dimethylaminobenzophenone).
  • Preferred mixtures are those of (A) a compound of the formula I in which X and Z are each hydrogen and the group --CO--Y is in the 1-position or 3-position, in particular those in which Y is --O--alkyl, --NH--alkyl or --N(alkyl)(alkyl), each having 1-4 C atoms in the moieties, and (B) an aliphatic tertiary amine, an alkyl p-dimethylaminobenzoate or Michler's ketone.
  • aliphatic tertiary amines are trimethylamine, triethylamine, tri-isopropylamine, tributylamine, dodecyl-dimethylamine, octyl-dimethylamine, triethanolamine, tris-(hydroxypropyl)-amine, N-methyl-diethanolamine or N-butyl-diethanolamine.
  • Particularly preferred mixtures are those of (A) a compound of the formula I in which X and Z are each hydrogen and the group --CO--Y is in the 1-position or 3-position, in particular those in which Y is --O--alkyl, --NH--alkyl or --N(alkyl)(alkyl), each having 1-4 C atoms in the alkyl moieties, and (B) triethanolamine or a C 1 -C 4 --alkyldiethanolamine.
  • the mixtures according to the invention preferably contain the compounds of the formula I and the organic amines in a weight ratio of 4:1 to 1:4.
  • photopolymerisable compounds are unsaturated monomers, such as esters of acrylic or methacrylic acid, for example methyl acrylate, ethyl acrylate, n- or tert.-butyl acrylate, isooctyl acrylate or hydroxyethyl acrylate, methyl methacrylate or ethyl methacrylate, ethylene diacrylate, butanediol diacrylate, hexanediol diacrylate, neopentyl diacrylate, trimethylolpropane trisacrylate, pentaerythritol tetraacrylate or pentaerythritol trisacrylate; acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and N-substituted (meth)-acrylamide; vinyl esters, for example vinyl acetate, vinyl propionate, vinyl acrylate or vinyl succinate; other vinyl compounds, such as vinyl esters,
  • the mixtures according to the invention are particularly suitable for the photopolymerisation of acrylic acid esters and mixtures thereof.
  • unsaturated acrylic resins include, for example, reaction products of polyepoxides (epoxy resins) with acrylic acid or methacrylic acid or reaction products of polyisocyanates with hydroxyalkyl acrylates and also the reaction products of hydroxyl group-containing polyesters or polyethers with acrylic acid or methyacrylic acid.
  • these unsaturated acrylic resins are used as a mixture with one or more acrylates of a mono-, di or poly-alcohol, for example ethyl acrylate, butyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate or 2-hydroxypropyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexamethylene diacrylate, trimethylolpropane trisacrylate or pentaerythritol tetraacrylate.
  • a mono-, di or poly-alcohol for example ethyl acrylate, butyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate or 2-hydroxypropyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexamethylene diacrylate, trimethylolpropane tri
  • the invention also relates to photopolymerisable systems consisting of (a) at least one ethylenically unsaturated compound, (b) a mixture of (A) and (B), as defined, and, if desired, (c) other additives, such as inhibitors, stabilisers, UV absorbers, fillers, pigments, dyes, agents for imparting thixotropic properties and levelling assistants, for example silicone oil.
  • additives such as inhibitors, stabilisers, UV absorbers, fillers, pigments, dyes, agents for imparting thixotropic properties and levelling assistants, for example silicone oil.
  • Inhibitors which are employed and which are intended to provide protection against premature polymerisation, in particular during the preparation of the systems by mixing the components, are, for example, hydroquinone, hydroquinone derivatives, p-methoxyphenyl or ⁇ -naphthols.
  • UV absorbers which can be employed are those of the benztriazole or benzophenone type.
  • Suitable fillers are, for example, silicic acid, talc or gypsum.
  • Preferred photopolymerisable systems are those in ratios of 99.5-80% by weight of (a) and (c) to 0.5-20% by weight of (b).
  • an acrylic acid ester or a mixture of several acrylic acid esters is used as component (a).
  • the photopolymerisable systems according to the invention are a printing ink or a white lacquer.
  • the initiator mixtures according to the invention are very important for the photocuring of printing inks and coatings containing white pigments, since the drying time of the binder is a decisive factor in determining the production speed of graphical products and should be of the order of magnitude of fractions of a second.
  • the initiators according to the invention are also very suitable for photocurable systems for the production of printing plates.
  • a further field of application is the UV curing of coatings on metal, for example in the lacquer coating of sheet metal for tubes, cans or bottle closures, and also the UV curing of plastic coatings, for example floor or wall coverings based on PVC.
  • UV curing of coatings on paper are the colourless lacquer-coating of labels, gramophone record sleeves or book jackets.
  • the mixtures according to the invention can also be used as initiators for photochemical crosslinking of polyolefines.
  • Suitable polyolefines are, for example, polypropylene, polybutene and polyisobutylene and also copolymers, for example ethylene/propylene copolymers, but preferably polyethylene of low, moderate or high density.
  • photoinitiators to the photopolymerisable systems is in general effected by simply stirring in, since most of these systems are liquid or readily soluble. Usually, the initiators dissolve, which ensures their uniform distribution and also transparency of the polymers.
  • Polymerisation is effected by the known methods for photopolymerisation, by irradiation with light rich in short-wave radiation.
  • Suitable light sources are, for example, medium-pressure, high-pressure and low-pressure mercury vapour lamps and also superactinic fluorescent tubes, the emission maxima of which are in the range between 250 and 450 nm.
  • the photoinitiator is added to the polyolefine before or during shaping, for example by mixing in powder form or by mixing with the plasticised polyolefine.
  • Crosslinking is effected by irradiation of the shaped article in solid form, for example in the form of films or fibres.
  • the compounds of the formula I, according to the invention, are also suitable as sensitisers for photocrosslinkable polymers of very diverse types.
  • Such polymers are used, for example, for the production of printing plates for the offset printing process, for the preparation of photo offset lacquers and for unconventional photography, for example for the production of photographic images by means of photopolymerisation or photocrosslinking.
  • Such polymers are used in particular as so-called photoresists for the production of printed circuits by methods known per se. For this purpose, that side of the printed circuit board which is provided with the light-sensitive coating is exposed through a transparent negative carrying the image of the printed circuit and then developed, after which the unexposed areas of the coating are removed by developer liquid.
  • Polymers which can be used are, per se, any desired materials for which the sensitivity to light (sensitivity towards actinic radiation) can be increased by the use of the compounds of the formula I, according to the invention.
  • the compounds of the formula I are very particularly suitable for sensitisers for polymers of the type described in German Offenlegungsschrift No. 2,626,769, i.e. polymers which contain, as light-sensitive groups, groups of the formula XVI ##STR18## in which G 1 and G 2 independently of one another are alkyl having 1-4 C atoms, especially methyl, or G 1 and G 2 together make up the members required to complete a 5-membered to 6-membered carbocyclic ring.
  • the compounds of the formula I can be incorporated in the photocrosslinkable polymers in a manner known per se.
  • the content of compounds of the formula I in the polymer can vary greatly depending on the intended use and the number of photocrosslinkable groups present in the polymer, but in general is between about 0.1 and 20%, based on the weight of the polymer.
  • This diester is refluxed in a solution of 28.0 g (0.5 mol) of potassium hydroxide in 500 ml of methanol for 1.5 hours, the reaction mixture is concentrated and 250 ml of water are added. The heterogeneous reaction mixture is washed with methylene chloride (3 ⁇ with 150 ml in each case), the aqueous phase is treated with active charcoal and filtered and the filtrate is concentrated. The filtrate is then acidified with concentrated sulfuric acid and the precipitate which has separated out is filtered off. After drying in vacuo at 80° C., 37.9 g (69% of theory) of 2-phenylthio-terephthalic acid remain; melting point >250° C.
  • 2-(4-Methylphenylthio)-terephthalic acid can also be prepared as follows: 90.2 g (0.726 mol) of p-thiocresol are dissolved in 600 ml of N,N-dimethylformamide, after which 31.7 g (0.792 mol) of finely powdered sodium hydroxide are added. After stirring for half an hour at 20°-25° C., 158.0 g (0.660 mol) of dimethyl nitroterephthalate are added to the homogeneous solution and the reaction mixture is stirred for 1.5 hours at 70° C. After cooling to 20°-25° C., 1000 ml of water are added and the precipitate which has separated out is filtered off. 275 g of moist product are obtained.
  • a blue printing ink is prepared in accordance with the following recipe: 55.0 parts by weight of Setalin AP 560 (acrylic resin from Synthese, Holland), 20.0 parts by weight of Irgalith GLSM (blue pigment from Ciba-Geigy), 4.0 parts by weight of a photoinitiator of the formula I, 4.0 parts by weight of N-methyldiethanolamine and 17.0 parts by weight of Ebecryl 150 (acrylic resin from UCB-Belgium).
  • a blue coloured paste is prepared from the Setalin AP 560 and the Irgalith GLSM on a three-roll mill.
  • the photocuring agent is predissolved with the amine in Ebecryl 150 and the resulting solution is incorporated in the blue coloured paste by dispersing on a muller machine.
  • the printing ink is then applied in a coating of 1.5 g/m 2 to special paper with the aid of a Prufbau proof press.
  • the sampler are cured in one pass by irradiating in a UV apparatus (manufacturer: Radiation Polymer Company USA) at a variable transport speed.
  • the set-off test is used to assess the curing.
  • the speed is determined at which no further transfer of printing ink to neutral paper can be determined under a printing pressure of 25 Kp/cm 2 .
  • the measured values obtained with the thioxanthone derivatives according to the invention are listed in the following table.
  • the numbers in the second column give the printing speed in m/second which is possible if no transfer of the printing ink is to result in the set-off test. The higher this speed, the more rapid is the curing of the printing ink.
  • the figures in the third column indicate the speed at which the abrasion test is passed.
  • a blue printing ink is prepared in accordance with the following recipe:
  • the coloured paste is prepared on a three-roll mill.
  • Photoinitiator solution 1 g of a photoinitiator of the formula I, 1 g of N-methyldiethanolamine and 2 g of Ebecryl 150.
  • Example I curing is evaluated by means of the set-off test and the abrasion test.
  • the measured values obtained for this printing ink recipe are listed in the following table.
  • a white lacquer is prepared in accordance with the following recipe: 1.94 g of PLEX 6631 (acrylic resin from Rohm & Haas, Federal Republic of Germany), 0.53 g of 2-hydroxypropyl acrylate, 2.47 g of titanium dioxide RTC-2 (titanium dioxide for Thioxide, England), 0.13 g of N-methyldiethanolamine, 0.26 g of a photoinitiator of the formula I and 1.02 g of hexanediol diacrylate.
  • the mixture, without hexanediol diacrylate, is twice ground for 200 revolutions with the aid of a muller machine under a weight of 7.5 kg.
  • the hexanediol diacrylate is then added to the ground mixture.
  • the white lacquer prepared in this way is applied to glass plates using a 40 ⁇ m doctor.
  • Wipe resistance The number of passes of the sample through the irradiation apparatus required to obtain a wipe-resistant surface is determined.
  • Pendulum hardness The samples are passed through the UV irradiation apparatus 10 times. The Konig pendulum hardness is then determined (DIN 53,157).
  • Yellowness index The samples are passed through the UV irradiation apparatus 10 times. The yellowness index is determined with the aid of a colour measuring instrument.
  • the solution is stabilised, while still hot, with 2.57 g of 2,6-di-tert.-butyl-p-cresol.
  • sensitiser indicated in Tables I, II and III, which follow are added to 100 g amounts of the polymer solutions described under (a).
  • Copper-laminated epoxide sheets are coated by whirl-coating (500 revolutions/minute for 1 minute) with the polymer solutions, which have been diluted to a 15% by weight solids content, in such a way that, after drying, a 1-3 ⁇ thick polymer coating is formed on the copper.
  • the coated sheets are exposed through a negative original (step wedge Stauffer 21-step sensitivity guide) as follows: using either a 400 Watt high-pressure mercury vapour lamp at a distance of 55 cm from the vacuum table or a 1000 Watt metal halide lamp at a distance of 60 cm from the vacuum table.
  • the image After exposure, the image is developed for 2 minutes in a 1,1,1-trichloroethanol bath, by which means the parts which have not been crosslinked are dissolved out.
  • the resulting relief image of the depicted step wedge is rendered more easily visible by etching the copper portions with a 50% FeCl 3 solution.
  • the thioxanthones according to the invention are distinguished by a markedly increased photosensitivity, in that approximately the same or even a greater number of steps can be rendered visible with substantially smaller amounts of sensitiser (amounts which are up to 50% smaller).
  • the thioxanthones according to the invention also have a higher relative sensitivity.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerization Catalysts (AREA)
  • Indole Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Plural Heterocyclic Compounds (AREA)
US06/392,922 1979-05-18 1982-06-28 Thioxanthonecarboxylic acid esters, thioesters and amides Expired - Fee Related US4506083A (en)

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CH467179A CH640849A5 (de) 1979-05-18 1979-05-18 Thioxanthoncarbonsaeureester, -thioester und -amide.
CH4671/79 1979-05-18

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US4791213A (en) * 1985-11-29 1988-12-13 Ward Blenkinsop & Company Limited 2-hydroxy-3-thioxathonyloxy-1-propanaminium salts
US5310909A (en) * 1989-11-29 1994-05-10 Ciba-Geigy Corporation Photochromic compounds, a process for their preparation, and their use
US5371115A (en) * 1984-02-10 1994-12-06 Ciba-Geigy Corporation Cationically polymerizable compositions containing iron metallolene salt
US6025408A (en) * 1997-03-27 2000-02-15 First Chemical Corporation Liquid thioxanthone photoinitiators
US20030229233A1 (en) * 2000-11-15 2003-12-11 Carsten Berg Process for the preparation of thioxanthones
US20050014860A1 (en) * 2001-10-18 2005-01-20 Herlihy Shaun Lawrence Multi-functional thioxanthone photoinitiators
US20050112086A1 (en) * 2003-11-26 2005-05-26 Surmodics, Inc. Biocompatible polymerization accelerators

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GB2108487B (en) * 1981-11-03 1985-07-31 Sericol Group Ltd Water soluble thioxanthone photoinitiators
US4615968A (en) * 1982-11-04 1986-10-07 Ciba-Geigy Corporation Compositions of matter which crosslink under the action of light in the presence of sensitizers
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US5371115A (en) * 1984-02-10 1994-12-06 Ciba-Geigy Corporation Cationically polymerizable compositions containing iron metallolene salt
US5494944A (en) * 1984-02-10 1996-02-27 Ciba-Geigy Corporation Hardenable composition and its use
US4791213A (en) * 1985-11-29 1988-12-13 Ward Blenkinsop & Company Limited 2-hydroxy-3-thioxathonyloxy-1-propanaminium salts
US5310909A (en) * 1989-11-29 1994-05-10 Ciba-Geigy Corporation Photochromic compounds, a process for their preparation, and their use
US5432049A (en) * 1989-11-29 1995-07-11 Ciba-Geigy Corporation Photochromic composition
US6025408A (en) * 1997-03-27 2000-02-15 First Chemical Corporation Liquid thioxanthone photoinitiators
US20030229233A1 (en) * 2000-11-15 2003-12-11 Carsten Berg Process for the preparation of thioxanthones
US7126011B2 (en) * 2000-11-15 2006-10-24 Prom Limited Process for the preparation of thioxanthones
US20050014860A1 (en) * 2001-10-18 2005-01-20 Herlihy Shaun Lawrence Multi-functional thioxanthone photoinitiators
US7354957B2 (en) * 2001-10-18 2008-04-08 Sun Chemical Corporation Multi-functional thioxanthone photoinitiators
US20050112086A1 (en) * 2003-11-26 2005-05-26 Surmodics, Inc. Biocompatible polymerization accelerators
US8202833B2 (en) 2003-11-26 2012-06-19 Surmodics, Inc. Composition containing biocompatible polymerization accelerator and polymerizable material

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JPH0135001B2 (ja) 1989-07-21
GB2119364A (en) 1983-11-16
FR2456741A1 (fr) 1980-12-12
GB2050378B (en) 1983-11-16
CH640849A5 (de) 1984-01-31
JPS55154970A (en) 1980-12-02
DE3018891A1 (de) 1980-11-27
US4505794A (en) 1985-03-19
GB2050378A (en) 1981-01-07
FR2456741B1 (ja) 1983-04-08
GB2119364B (en) 1984-04-11

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